Protein dispersions and their use in printing inks



- by exposure tosteam.

This invention relatesto printing inkssand more particularly to printing inks which harden Printing inks which harden by'the application of moisture in thefor-m of steam 'or water, consist of compositions made from :a. water-miscible liquid such as ethylene glycol, diethylene glycol or the like, in which there is dispersed a waterinsoluble binder such as zein, a, resin and a c'o1or-.

ing material such as a pigmentof the character of carbon black, chrome yellow or the.l1ke, or a dyestuff. The hardening of the ink is caused by exposing a printed illm to steam or water. I During the process of setting, thewater-miscible liquid absorbs sufficient water to causethe-precipita-v tion of the binder and the pigment." 'Due to the nature of the process, it is necessary for the binder to be sumciently moisture-sensitive so that the addition of water to the organic liquid causes its separation, but the binder should have an adequate tolerancefor moisture so that it will not prematurely precipitate. I

Usually inks made with zein are toosensitive to high humidities, such as about 50 resulting inja breakdown on the printing press, with conse quent failure of proper distribution on the rollers and the resultant failure of the printingprocess;

Printinginksmadeby suspending. coloring materials'in a'colloidal dispersion of from to 35% of soybean proteins, s'aidproteins containing from 95% upwards of pure protein. dispersion 'in diethylene glycol, using 6% of guanicline-earbonate.

asthe dispersing agent, and made up to an apparent viscosity of 10 to poises as desc 'ibedby .Schmutzler and Othmer, Industrial andEngineering Chemistry, 1196-1202 1943),'have'a tolerance for moisture and therefore, as contrasted with zein proteininks'do'not break down on the press at high humiditiesand satisfactorily harden if their printed filmstare exposed to steam;

They may be used where water resistance oflthe printed film is not a 'factor of paramount1',im

portance. This soybean-protein diethylene glycol dispersion .can be used with highjoil absorptio pigments, suchas carbon 7 low, Prussian blue and. the'like;

black','1benzidene yel- Printing inks prepared. rrom' colloidaldispersionsfof other vegetable proteinssuch'as alka-' line extracted corn proteins, cottonseed globulin, I hempseed globulin or thellike, made up as, the

soybeanipr otein ink above described to similar concentrations in diethyleneglycol'witha cor responding amount of peptizingagent, resemble th soybeanprotein inks in charact t and m qrmance.

Alfred E S chmutzler, Teaneck, N. J., and

V 1 Donald F.-Qthmcr,.icoudersport','Pa.

a Noprawm Application October 27,1944, smauv maus,

' i RElSSUED '1 mm USE IN Jum 2 195 8523382 Printing-inks made from dispersions of casein and other'protein's of animal origin such as blood albumin, gelatin or the like, in polyhydric alcohols set to harder films than those made from soybean 5 protein. -When the protein dispersions are made up to viscosities higher than 30 poises, they are found ,to possess greater binding characteristics than the lower viscosity dispersions.

It is alsoto be' noted that printing inks made 10 of thejforegoing materials are usually alkaline in character. The alkalinity of the dispersions is a disadvantage as it sometimes causes a change in the hue of the coloring materials and sometimes efiects the light-fastness thereof.

If thehigh viscosity dispersions are acidified, there is a decrease in the water absorption of the 'dry, ink films. All colloidal dispersions of these proteins, as contrasted with zein, may be blended with resins 2 resulting in improved consistency of the ink as .well as improved resistance of the printed film. In blends with resins, the protein dispersions usually impart hardness and moisture tolerance to theprint g inksand sometimes plastic flow. 2 Resinous materials such as long polymerized phenol modified indene coumarone resin, a. complex phenolic-compound of the group comprisin partially polymerized phenol modified indene coumaroneresins, alkyd resins, urea formalde- 30 hyderesins, rosin or the like, may be used for such purposes. 1

;If neutralized or slightly acid dispersions are to be used instead of the alkaline dispersions, it is advantageous to effect the neutralization or 3 slight acidification of the alkalinepeptizing agents abietic, maleic or fumaric. acid modified rosin, 40 linseed oil fatty-acid, acidic, compounds as obtained by reacting the equivalent of one molecular. weight, of adibasic acid with the equivalent of 'one molecular weight :of a dihydric alcohol or the like, may' be used ioriacidifying purposes. 5 We have also. found that the alkaline dispersions mayibe neutralized by the-action of phenol, cresol,

\ other phenols, phenol alcohols, phenyl isothiothe dispersions when reacted" with dibasic acids -suchas maleic'acid or its anhydride, fumaric acid or' the like, form softres'inswhich have a tendency, to harden by oxidation. 3 The alkyd resins as well as the proteins possess a high tolerance for moisture, and in case of printing made therefrom the contribution of the cyanate or' the like. The polyhydricalcohols of I ant films when the printed films are exposed to moisture.

Another object of this invention is to provide for the economical production of dispersions which may be used for preparing printing inks.

an m! creasing hardness. In other compositions such rollerink milLy' x Y i [2 Y Guanidine v Diethylenefg lycol l {EmmpleVII"" w l- Acid cas nifllyfl' 1 Guanidine'fcarbonate"-' Diethylenegly 01 are heatedat 0 mason-eds this tem The foregoing and other objects may be ac-'- complished by using dispersions of which th iollowing are illustrative embodiments:

Example! hour. '1he"=veh ic1e-is:mimed into'an Y b ms t I PM s narachutes: v p; 1 Soy can pro con aining mm a upj s j wards oi. pure protein 20 f Guanidine' carbonate 3 I p f, v Dicyandiamide 3' .'2 %fs0ybeanfprotein- Diethylene glycol 7 from-95%upwards oi-mmeprotein'as pre-,

are heated while stirring to 125-130 0. in about 15 minutes, held at this temperature for about 2 hours, then carefully the temperature is raised to 140 C. in about 15 minutes and held to 140- perature, of about 200 to 1 hour).

The resulting dispersion is mixed and milled with a coloring material, such as 25 parts car- "0 bon black.

Example II The dispersion, as prepared in Example I, is-

neutralized with glacial acetic acid (about 4 are heated while stirring to 130 C. in about 20 minutes and held between 130-135" .C. to a viscosity at room temperature of about 300 poises (about 1% to 2 hours), then, at 130-135 C.

milled with 1 00 parts I 9 are meta tases titer sultingdispe'rsionis This vehicle is mixed and chrome yellow.

Example Iv The dispersion,- as prepared in Example 111, j

is neutralized with glacial acetic acid (about 4 parts). After cooling, it is mixed and milled v with parts Prussian blue. 66 1 v .j' 1

Example V r soybean wid ns $1.19?

g P pureproteihoontent..-

Casein Ethylene diamine Guanidine carbonate "L... 2 70 Ethylene, 9 Diethylene glycol 78 reheated while stirringtl'at O; or are heated, while stirring, for 3 hours at 8010. the,

'I'oward'the end of this time, 2 parts acetic anhydride are added, drop by "drop. After cooling,

,5 parts carbon black are mixed with the dis- 7; Phthalic mmfi 145 c. to an apparent viscosity, at room tem- 35 D0ises.(a-bout 30 minutes arefheated,'while at no c.

hy d Z d dr and t ,is iraised to'130 140',Gain'about tenminutes-"and. heidjthere10 e.,hour.;-Arte co iinggit is. r.

"Wi -#9 l h l r mixed'fandmines Lure tori-119m;

are heated at 140 C. for

mixture-is reacted for '1 hour. p rsion' is I milled Diethylene glycol 7 Carbon-black Epamplc'IZ l Soybean. protein havirig from %upi8tds pure protein contenta...--.. Methylamlne (crude) Diethylene glycol are heated, whilejstirring,=itois minutes, hcidzat'this C. inabout lli'ininutesv peraturefor-zfhours At period I Maleic'anhydrhde, A soft phenolic-:modifi ,Ied anq a d-W1 1 1 Rosin fao 'iinutesj nen' 10' I parts phthalic' acid anhydride addedand the or f hour, then-carefi yx heitempemm I a are added and the mixture is contlnue'd to be heated at 140 C. for 3 hours,

I Parts Diethylene glycol 60 Carbon black 60 are mixed with this dispersion and the mixture is milled into an ink.

Example XI 100 parts of 20% soybean protein dispersion con- I taining from 95% upwards of pure protein,

prepared in Example III 5 parts diethylene glycol soluble pure phenolformaldehyde resin, dissolved 'in i parts triethylene glycol are heated at 140 C. for 20 minutes, then 30 parts of phthalic anhydride are added and the mixture is heated for 1 hour at 130-140 C. This disperare mixed well, and heated to 135 C. in 30 minutes and kept between 135-145 C. while stirring and adding 2 Parts Rosin ,10 Phthalic anhydride 90 and the mixture is held between 135-145 C. for 2 hours. Then it is diluted with 60 parts diethylene glycol. The resulting vehicle is mixed and milled with 100 parts lithol red.

Example XIII Parts Soybean having from 95% upwards of pure protein content 30 Guanidine carbonate 3 Ethylene glycol 6'7 heated to 125 C. in hour, held at 120-130 C. for 2 hours, then Parts Phthalic acid anhydride 84 Rosin 8 are added and heated for 1 hour between 130-140" C. While cooling, below 110 C., the viscous ve- Example!!! Casein 30 Ethylene dia'ir 2 Ethylene glycol 68 are heated to 110- 0. in about 30 minutes, at 110 0., add,

' Parts Rosin G 10 Phthalic anhydride 90' -are propylene glycol-dipropylene and tetrahicle is thinned with 50 parts diethylene glycol.

The vehicle is mixed and milled with 300 parts ethylene glycol. The various glycols of the olefines described herein may be designated as "alklylene glycols.

Pigments and coloring materials either of 'phthalic anhydride, maleic a '"lhydride, acetic acid,

ammonium sulfate, am mcxalate, aniline, phenol, nitroethane, nitroprepane, nitrobenzene. calcium hydroxide, urea, thiourea and 2-nitro-= 2-methyl-1,3-propanediol. The foregoing compounds and those heretofore described in the examples may be designated as peptizing agents.

Having described our invention, we claim:

1. A dispersion consisting of a soybean protein containing from 95% upwardstof-pure protein, a polyhydric alcohol selected from the group consisting of ethylene glycol and diethylene glycol, and a protein peptizing agent, said peptizing agent being guanidine carbonate.

2. A dispersion consisting ofa soybean protein containing from 95% upwards of pfireprotein, diethylene glycol, a peptiging agent, the P ptizing agent being guanidine carbonate} and a pigment. f

3. A dispersion consistingpf a soybean protein containing from 95% upwards of pure protein,

dispersed in a polyhydric alcohol, a resin, a peptizing agent and a pigment; wherein the polyof chrome yellow. v

' Example XIV I Parts Casein 40 Ethylene diamine 6 Ethylene glycol 54 at 130-140 0.. for two hours, then it is'cooled and parts diethylene glycol are added. This' dispersion, after cooling is mixed and-milled with 250 parts chrome yellow.

hydric alcohol is selected from the grou'pfleonsisting of ethylene glycol and diethylene glycol, the peptizing agent being guanidine'carbonate. 4

4. A printing ink essentially consisting of a dispersion of soybean protein containing from upwards of pure protein in diethylene glycol, the said protein being peptized by the action of guanidine carbonate; a resin and a pigment.

'5. A printing ink essentially consisting of a dispersion of a soybean protein having from 95% upwards of pure protein in diethylene glycol, the said protein being P DtiZed by the action of 76 guanidine carbonate, and a pigment.

6. A dispersion consisting of a soybean protein containing from 95% upwards of pure protein, ethylene glycol, a peptizing agent, the peptizing agent being guanidine carbonate, and a pigment.

7. A printing ink essentially consisting of a 5 dispersion oi. soybean protein containing from 95% upwards of pure protein in ethylene glycol,

the said protein being peptized by the action of guanidine carbonate; a resin and a pigment.

8. A printing ink essentially consisting of a dispersion of a soybean protein having from 95% upwards of pure protein in ethylene glycol, the

said protein being peptized by the action of guanidine carbonate, and a pigment.

ALFRED F. SCHMUIZLER. WADONALD F. OTHMER.

8 nnmnnncns one The following references are of record in the file of this patent:

- UNITED ,sTA'rEs PATENT OTHER REFERENCES Industrial 8: Engineering Chemistry, Nov. 1943, pages 1196 to1202. 

